CN1724247A - Carbon fiber composite material and manufacturing method - Google Patents
Carbon fiber composite material and manufacturing method Download PDFInfo
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- CN1724247A CN1724247A CNA2005100720554A CN200510072055A CN1724247A CN 1724247 A CN1724247 A CN 1724247A CN A2005100720554 A CNA2005100720554 A CN A2005100720554A CN 200510072055 A CN200510072055 A CN 200510072055A CN 1724247 A CN1724247 A CN 1724247A
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- thermoplastic resin
- carbon
- fiber
- fibre composite
- carbon fibre
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 176
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
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- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 39
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
- Y10T428/249945—Carbon or carbonaceous fiber
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The present invention obtains a carbon fiber composite material having uniformly dispersed carbon nanofibers and to provide a method for producing the same, to obtain a carbon fiber composite metal material and to provide a method for producing the same, and to obtain a carbon fiber composite nonmetal material and to provide a method for producing the same. The carbon fiber composite material 4 comprises a thermoplastic resin 30, carbon nanofibers 40 dispersed into the thermoplastic resin 30 and particles 50 for dispersion, promoting dispersion of the carbon nanofibers 40 into the thermoplastic resin 30.
Description
Technical field
The present invention relates to carbon fibre composite and manufacture method thereof, carbon fiber-metal composite material and manufacture method thereof, carbon fiber composite non-metallic material and manufacture method thereof.
Background technology
In recent years, use the composite of carbon nano-fiber extremely to gaze at.Because such composite comprises carbon nano-fiber, so people expect that it can improve performances (for example, opening the 2003-239171 communique with reference to the spy) such as mechanical strength.
In addition, casting method as metallic composite, have in the prior art and make magnesium vapor permeate, be dispersed in the porous molded body that forms by oxide ceramics, simultaneously, make the casting method (for example, with reference to spy open flat 10-183269 communique) of molten metal infiltration by importing nitrogen at porous molded body.
But, because carbon nano-fiber has very strong coherency each other, so be difficult to make carbon nano-fiber to be evenly dispersed in the base material of composite.Therefore, be difficult to obtain to have the carbon nano-fiber of desired characteristic now, and, carbon nano-fiber with high costs can't efficiently be utilized.
In addition, prior art make the casting method of molten metal infiltration in the porous molded body that forms by oxide ceramics, also because complex process, so be difficult to carry out industrial production.
Summary of the invention
Therefore, the objective of the invention is to, a kind of carbon fibre composite and manufacture method thereof of even dispersed carbon nanofiber is provided.In addition, the present invention also aims to, a kind of carbon fiber-metal composite material and manufacture method thereof of even dispersed carbon nanofiber is provided.And, the present invention also aims to, a kind of carbon fiber composite non-metallic material and manufacture method thereof of even dispersed carbon nanofiber is provided.
The carbon fibre composite that the present invention relates to comprises: thermoplastic resin, be dispersed in the carbon nano-fiber in the described thermoplastic resin and promote the dispersion particle that carbon nano-fiber disperses in described thermoplastic resin.
In carbon fibre composite of the present invention, based on reason described later, carbon nano-fiber is evenly dispersed in the base material thermoplastic resin more.Even the difficult especially diameter that disperses is about the carbon nano-fiber smaller or equal to 30nm, perhaps the carbon nano-fiber of curved fiber shape also can be evenly dispersed in the thermoplastic resin.
Thermoplastic resin of the present invention is that general employed heating back is embodied degree of plasticification, cooling back the plastics that solidify are taken place, and does not comprise the rubber composition of thermoplastic elastomer (TPE) etc. here.Carbon nano-fiber is very difficult to disperse in thermoplastic resin; but; in the present invention, the dispersion by metallic particles or non-metallic particle etc. promotes that with particle the dispersion of carbon nano-fiber, its effect are to can be implemented in the thermoplastic resin evenly dispersed carbon nanofiber.
In addition; the same with carbon fibre composite; the described thermoplastic resin of the carbon fibre composite that the present invention relates to metal or nonmetal basal body material substitution, formed carbon fiber-metal composite material or carbon fiber composite non-metallic material also can be evenly dispersed in wherein carbon nano-fiber by metallic particles or non-metallic particle.
The manufacture method of the carbon fibre composite that the present invention relates to comprises:
Operation (a), the dispersion particle of mixed thermoplastic resin and promotion dispersion of carbon nano-fiber in this thermoplastic resin; Operation (b) comprising described dispersion with in the described thermoplastic resin of particle, is mixed described carbon nano-fiber, and is made its dispersion by shearing force.
By manufacture method of the present invention, comprise the thermoplastic resin that disperses with particle owing to use, when utilizing shearing force dispersed carbon nanofiber, disperse flowing with the turbulent condition that thermoplastic resin can take place around the particle.Carbon fibre composite of the present invention can further promote the dispersion of carbon nano-fiber in the base material thermoplastic resin by this flowing, thereby carbon nano-fiber is evenly dispersed in the thermoplastic resin.Even the difficult especially diameter that disperses is about the carbon nano-fiber smaller or equal to 30nm, perhaps the carbon nano-fiber of curved fiber shape also can be evenly dispersed in the thermoplastic resin.
The operation (b) of utilizing shearing force that carbon nano-fiber is dispersed in the described thermoplastic resin can use following method to carry out: (1) open type roller method, the mixing method of (2) closed, (3) multiaxis push mixing method, etc.
In addition, the manufacture method of the carbon fiber-metal composite material that the present invention relates to can also comprise the operation (c-1) that the described thermoplastic resin of described carbon fibre composite is replaced into metal matrix material.
In addition, the manufacture method of the carbon fiber composite non-metallic material that the present invention relates to can also comprise the operation (c-2) that the described thermoplastic resin of described carbon fibre composite is replaced into the nonmetal basal body material.
Like this described operation (c-1) or described operation (c-2) can adopt following method: (4) are with the powder compacting method of carbon fibre composite powder compacting (comprising powdered-metal), (5) carbon fibre composite is blended into motlten metal or fusion nonmetal in, the casting of in mold, casting with the shape of wishing formation, (6) above carbon fibre composite, place metal derby or nonmetal (placement step), and make its fusion become motlten metal or fusion is nonmetal by heating described metal derby or nonmetal, simultaneously, make the described thermoplastic resin volatilization in the described carbon fibre composite, and make motlten metal or fusion is nonmetal permeates, thereby described thermoplastic resin is replaced into described motlten metal or the nonmetallic osmosis of described fusion, or the like.
The manufacture method of such carbon fiber-metal composite material or carbon fiber composite non-metallic material, because the carbon nano-fiber that adopts the front to narrate evenly disperses carbon fibre composite wherein, can obtain by disperseing to make even dispersed carbon fiber-metal composite material of carbon nano-fiber or carbon fiber composite non-metallic material with particle.
In addition, at so described operation (c-1) or the described matrix material in the described operation (c-2), can adopt and the described dispersion identical material of particle.
Particularly by adopting the osmosis of described (6), with the nonmetal carbon fibre composite that contacts of motlten metal and fusion, utilize fused solution that thermoplastic resin is permeated in thermal decomposition, so under the homodisperse state of carbon nano-fiber, just fused solution can be replaced into cakey metal or nonmetal, and cast.In carbon fibre composite, with respect to thermoplastic resin 100 weight portions, disperseing with particle is the 1-2000 weight portion, is preferably the 20-1000 weight portion.If disperse with particle below 1 weight portion, then dispersion effect is low, or capillarity is weak and motlten metal or the nonmetallic seepage velocity of fusion are slow, therefore considers to be difficult to adopt such dispersion particle from the aspect of productivity and cost.In addition, if disperse with particle more than 2000 weight portions, when making carbon fibre composite, will become is difficult to be impregnated into thermoplastic resin.
Description of drawings
Fig. 1 is a structural representation of making the device of carbon fiber-metal composite material by non-pressurised osmosis.
Fig. 2 is a structural representation of making the device of carbon fiber-metal composite material by non-pressurised osmosis.
The specific embodiment
Below, with reference to accompanying drawing embodiments of the invention are elaborated.
The related carbon fibre composite of embodiments of the invention comprises: thermoplastic resin, the dispersion particle that is dispersed in the carbon nano-fiber in the described thermoplastic resin and promotes the dispersion of carbon nano-fiber in described thermoplastic resin.
In addition, by the thermoplastic resin of described carbon fibre composite and the matrix material of metal are replaced, can obtain carbon fiber-metal composite material involved in the present invention.
And, by the thermoplastic resin and the nonmetallic matrix material of described carbon fibre composite are replaced, can obtain carbon fiber composite non-metallic material involved in the present invention.
The manufacture method of carbon fibre composite involved in the present invention, comprise: operation (a), mixed thermoplastic resin and the dispersion particle that is used for promoting that carbon nano-fiber disperses at this thermoplastic resin, and operation (b), carbon nano-fiber is blended in comprises described dispersion, and utilize shearing force to make its dispersion with in the described thermoplastic resin of particle.
The manufacture method of carbon fibre composite involved in the present invention also comprises: operation (c-1), the described thermoplastic resin of the carbon fibre composite that will obtain by above-mentioned manufacture method and the matrix material of metal are replaced.
The manufacture method of carbon fibre composite involved in the present invention also comprises operation (c-2), and the described thermoplastic resin and the nonmetallic matrix material of the carbon fibre composite that will obtain by above-mentioned manufacture method are replaced.
Thermoplastic resin for example preferably have with the compatibility height of carbon nano-fiber, have certain-length molecular length, have characteristics such as flexibility.In addition, make carbon nano-fiber be dispersed in operation in the thermoplastic resin, preferably carry out mixing with high as far as possible shearing force by shearing force.
(A) thermoplastic resin
The thermoplastic resin preferred molecular weight is 10,000 to 1,000,000, more preferably 50,000 to 300,000.Because if the molecular weight of thermoplastic resin is in this scope, the mutual complexing of thermoplastic resin molecule (combination) interconnects, so the carbon nano-fiber that thermoplastic resin invades cohesion easily each other, the effect of therefore separating carbon nano-fiber is remarkable.When the molecular weight of thermoplastic resin less than 10,000 the time, the complexing fully mutually of thermoplastic resin molecule is cut shearing force even if apply in the operation in the back, the effect of dispersed carbon nanofiber is also less.In addition, when the molecular weight of thermoplastic resin greater than 1,000,000 the time, thermoplastic resin is too hard, processing is difficulty.
By adopting Hahn's echo (Hahn echo) method of PULSED NMR, thermoplastic resin is in the temperature of described operation (b) (under the situation of ABS resin, for example be 250 ℃) under, the spin-spin relaxation time (T2s) of (detected) first composition was preferably for 100 to 50000 μ seconds.Because have the spin-spin relaxation time (T2s) of first composition of above-mentioned scope, so thermoplastic resin can be very soft and be had a very high transport properties of molecules.
Therefore, when mixed thermoplastic resin and carbon nano-fiber, thermoplastic resin can easily invade between the mutual slit of carbon nano-fiber by higher molecular motion.The spin-spin relaxation time (T2s) of first composition, if thermoplastic resin just can not have sufficient transport properties of molecules shorter second than 100 μ.In addition, the spin-spin relaxation time (T2s) of first composition, if it is easy to be mobile as liquid that thermoplastic resin will become longer second than 50000 μ, thereby be difficult to make the carbon nano-fiber dispersion.
By the spin-spin relaxation time that the Hahn's echo method that adopts PULSED NMR obtains, be the yardstick of the transport properties of molecules of expression material.Specifically, if the spin-spin relaxation time of thermoplastic resin is measured by the Hahn's echo method that adopts PULSED NMR, then can detect have relaxation time first composition of short spin-spin relaxation time (T2s), and have relaxation time second composition of long spin-spin relaxation time (T21).First composition with spin-spin relaxation time (T2s) is equivalent to the lower composition of high molecular transport properties of molecules (molecule of the skeleton), and second composition with spin-spin relaxation time (T21) is equivalent to high molecular transport properties of molecules than the higher composition (composition that is limited by the molecule of the skeleton key not.And the spin-spin relaxation time that we can say first composition, the short molecule motility was low more more, and thermoplastic resin is hard more.In addition, the spin-spin relaxation time of first composition, long more transport properties of molecules was high more, and thermoplastic resin is soft more.
As the determination method in the PULSED NMR, not only can be Hahn's echo method, also can be suitable for three-dimensional echo method, CPMG method (Carr-Purcell-Meiboom-Gill method) or 90 ° of impulse methods.But because carbon fibre composite involved in the present invention has the moderate spin-spin relaxation time (T2), Hahn's echo method is the most suitable.General three-dimensional echo method and 90 ° of impulse methods are suitable for measuring short T2, and Hahn's echo method is suitable for measuring moderate T2, and the CPMG method is suitable for measuring long T2.
In the temperature of the described operation (b) that determines by the Hahn's echo method that adopts PULSED NMR, the preferred spin-lattice relaxation time of thermoplastic resin (T1) was 10 to 5000m seconds.Because have the spin-lattice relaxation time (T1) of above-mentioned scope, thermoplastic resin can be very soft and be had a high transport properties of molecules.Therefore, when mixed thermoplastic resin and carbon nano-fiber, can easily invade between the carbon nano-fiber slit each other by high molecular motion thermoplastic resin.The spin-lattice relaxation time (T1), thermoplastic resin just can not have sufficient transport properties of molecules if shorter second than 10m.In addition, the spin-lattice relaxation time (T1), it is easy to be mobile as liquid that thermoplastic resin will become if longer second than 5000m, thereby be difficult to make the carbon nano-fiber dispersion.
The spin-lattice relaxation time (T1) that determines by the Hahn's echo method that adopts PULSED NMR is the same with the spin-spin relaxation time (T2) to be the yardstick of representing the transport properties of molecules of material.The spin-lattice relaxation time that we can say thermoplastic resin particularly, the short molecule motility was low more more, and thermoplastic resin is hard more, and the spin-lattice relaxation time, long more transport properties of molecules was high more, and thermoplastic resin is soft more.
Carbon nano-fiber usually its side by the hexatomic ring of carbon atom constitute, terminal five-membered ring and the closed structure of importing, still,,, on its part, generate atomic group or functional group easily so be easy to generate defective in the reality because there is structural unreasonable part.In the present embodiment, because at least one in main chain, side chain and the terminal chain of thermoplastic resin has the polar group very high with the atomic group compatibility of carbon nano-fiber, so can realize combining of thermoplastic resin and carbon nano-fiber.Thereby the cohesiveness that can overcome carbon nano-fiber makes it be easy to more disperse.
Can adopt the thermoplastic resin of polyethylene, polypropylene, poly-durol, polyvinyl chloride, polychlorostyrene ethenylidene, ABS resin, polystyrene, acrylonitrile-styrene resin, methacrylic resin, polyvinyl alcohol, EVA, polyamide, polyacetal resin, polycarbonate resin, mylar, polytetrafluoroethylene (PTFE), fluororesin, poly-imines, polyamide-imide etc. and the mixture of these materials as thermoplastic resin.
(B) disperse to use particle
To disperse to mix, be dispersed in the thermoplastic resin, can when mixing carbon nano-fiber, promote the dispersion of carbon nano-fiber in thermoplastic resin, and make it realize more well disperseing with particle.Can adopt metallic particles or non-metallic particle as disperseing with particle.
Can adopt aluminium and alloy, magnesium and alloy thereof, titanium and alloy thereof etc. to be commonly referred to as particle monomer or its combination of light metal as metallic particles.
Can adopt aluminium oxide (Al as non-metallic particle
2O
3), zirconia (ZrO
2), silicon nitride (Si
3N
4) particle monomer or its combination such as the pottery that waits or glass.
For promoting the dispersion of carbon nano-fiber, the average diameter of disperseing to be preferably greater than employed carbon nano-fiber with the average grain diameter of particle.In addition, disperseing the average grain diameter with particle is smaller or equal to 500 μ m, is preferably 1～300 μ m.When adopting non-pressurised osmosis in casting process, with respect to thermoplastic resin 100 weight portions, disperseing the amount with particle is 1～2000 weight portion, is preferably 20～1000 weight portions.If disperseing with particle is below 1 weight portion, because dispersion effect is low, and a little less than the capillarity, the nonmetallic seepage velocity of motlten metal or fusion is slow, so, consider to be difficult to adopt from the aspect of productivity and cost.In addition, if dispersion is more than 2000 weight portions with particle, when making carbon fibre composite, just be difficult to be impregnated in the thermoplastic resin.In addition, disperse to be not limited only to form of spherical particles with coating of particles, so long as when mixing disperse with particle turbulent shape flowable state shape takes place on every side, it can also be tabular, flakey.
Be under the situation of alumina particles for example, when making molten aluminum that infiltration take place, be thermal decomposited the oxide on the reduction alumina particles surfaces such as atomic group of generation by thermoplastic resin, can improve the wellability of alumina particles and molten aluminum, strengthen adhesion at metallic particles.In addition, since the mobile carbon nano-fiber that makes that the infiltration of molten aluminum causes invade in the alumina particles.Like this when disperseing with particle when the alumina particles surface has oxide, will have above-mentioned good effect.
(C) carbon nano-fiber
The carbon nano-fiber average diameter is preferably 0.5 to 500nm, for the intensity that improves carbon fibre composite more preferably 0.5 to 30nm.And carbon nano-fiber both can be that the fibers straight shape also can be the curved fiber shape.
The cooperation of carbon nano-fiber (adding) amount is not particularly limited, and can set according to purposes.The carbon fibre composite of present embodiment both can be used as thermoplastic resin material and had used, and perhaps used as the raw material with metal or nonmetal composite as matrix material.When the carbon fibre composite of present embodiment uses as the raw material with metal or nonmetal composite as matrix material, can comprise the carbon nano-fiber of 0.01～100 weight portion with respect to thermoplastic resin.When mixing carbon nano-fiber in metal or nonmetallic matrix material, the supply source of carbon nano-fiber can be used for related raw material with metal or nonmetal composite as matrix material, promptly uses as so-called masterbatch.
Can enumerate so-called CNT etc. as carbon nano-fiber.CNT comprises that the graphite sheet of carbon hexagonal wire side is closed into single layer structure cylindraceous or these cylindrical structures are configured to canular sandwich construction.That is, CNT both can only be made of single layer structure, also can only be made of sandwich construction, can also comprise single layer structure and sandwich construction simultaneously.And, can also use part to comprise the material with carbon element of carbon nano tube structure.In addition, except that the such title of CNT, can also name with the such title of graphite fibrillation nanotube.
Single-layer carbon nano-tube or multilayer carbon nanotube can be made desired size by arc discharge method, laser ablation method, vapour deposition process etc.
Arc discharge method is a kind of under the subatmospheric slightly argon or hydrogen atmosphere of pressure, carries out arc discharge between the electrode material made from carbon-point, thereby obtains being piled up in the method for the multilayer carbon nanotube on the negative electrode.In addition, single-layer carbon nano-tube is from catalyst such as mixed Ni/cobalts described carbon-point and after carrying out arc discharge, is attached to obtain in the carbon black on the container handling medial surface.
The laser ablation method is a kind of in rare gas (for example argon), by making carbon surface fusion, evaporation to the intense pulse laser as the carbon surface irradiation YAG laser that is mixed with catalyst such as nickel/cobalt of target, thereby obtains the method for single-layer carbon nano-tube.
Vapour deposition process is hydrocarbons such as pyrolysis benzene, toluene in gas phase, and synthesizing carbon nanotubes more specifically, can be enumerated flowing catalyst method, Zeolite support catalyst method etc.
Carbon nano-fiber carried out surface treatment in advance before mixing with elastomer, for example, inject processing, sputter etching processing, plasma treatment etc. by carrying out ion, can improve and elastomeric cohesive, wellability.
(D) in thermoplastic resin, mix carbon nano-fiber, and make the operation (b) of its dispersion by shearing force
In the present embodiment, as making metallic particles and carbon nano-fiber be blended in operation (a) and operation (b) in the thermoplastic resin, the example that has adopted multiaxis to push mixing method is narrated.
At first, in first loading hopper of two-axis extruder, add granular thermoplastic resin, utilize the shearing force thermoplastic resin generation fusion of the rotation generation of twin-screw (twin shaft).Disperse to use particle to the thermoplastic resin adding that is in this molten condition from second loading hopper of two-axis extruder, and then make the twin-screw rotation.Like this, implement thermoplastic resin and be used for promoting the operation (a) that carbon nano-fiber mixes with particle in the dispersion of the dispersion of this thermoplastic resin.
Then, from this thermoplastic resin and disperse with particle mixed the 3rd loading hopper of two-axis extruder add carbon nano-fiber, make the double-shaft spiral rotation, contain dispersion with in the described thermoplastic resin of particle thereby implement that described carbon nano-fiber is blended in, and make the operation (b) of its dispersion by shearing force.
Like this, high shearing force acts on thermoplastic resin, by this shearing force the carbon nano-fiber that has condensed can be separated from each other like one one ground extraction, thereby be dispersed in the thermoplastic resin, and the shearing force that produces by double-shaft spiral makes the dispersion that is dispersed in the thermoplastic resin with flowing of turbulent shape taken place around the particle.Mobile carbon nano-fiber by this complexity further is dispersed in the thermoplastic resin.
In addition, before mixing disperseed with particle, if earlier thermoplastic resin and carbon nano-fiber are mixed, the motion of thermoplastic resin will be limited by carbon nano-fiber, so, mix and disperse will become difficult with particle.Therefore, preferably in thermoplastic resin, implement to mix the operation (a) of disperseing before the adding carbon nano-fiber with particle.
In addition, in operation (b),, near the melting point temperature of employed thermoplastic resin, implement the mixing of thermoplastic resin and carbon nano-fiber in order to obtain high as far as possible shearing force.Be set at the average grain diameter of being wider than dispersion usefulness particle by interval, can be advantageously implemented in the dispersion of carbon nano-fiber in the thermoplastic resin double-shaft spiral.
At this moment, because the thermoplastic resin of present embodiment has above-mentioned feature, it is the feature of the molecular conformation (molecular length), molecular motion etc. of thermoplastic resin, thereby can easily realize the dispersion of carbon nano-fiber, therefore, can obtain to have the carbon fibre composite of good dispersiveness and dispersion stabilization (carbon nano-fiber is difficult to condense once again).More particularly, when thermoplastic resin is mixed with carbon nano-fiber, have the molecular length of appropriateness and the thermoplastic resin of higher transport properties of molecules and invade between the carbon nano-fiber, the polar group of thermoplastic resin combines with the atomic group of carbon nano-fiber.In this state, if strong shearing force is acted on the mixture of thermoplastic resin and carbon nano-fiber, the mobile carbon nano-fiber that is accompanied by thermoplastic resin also is moved, and the carbon nano-fiber that has condensed is separated, is dispersed in the thermoplastic resin.
In addition, owing to comprise the dispersion particle of scheduled volume in the thermoplastic resin, by being created on mobile as several bursts of complexity of turbulent flow that disperses with circumgranular thermoplastic resin, shearing force is also had an effect drawing back on the direction of each carbon nano-fiber.Therefore, even diameter is about smaller or equal to the carbon nano-fiber of 30nm or the carbon nano-fiber of curved fiber shape,, also can be evenly dispersed in the thermoplastic resin owing to move to each flow direction of thermoplastic resin molecule.
Make carbon nano-fiber be dispersed in operation in the thermoplastic resin by shearing force, have more than and be defined in above-mentioned multiaxis and push mixing method, also can adopt mixing method of closed or the mixing method of open type roller.In a word, so long as in this operation, it is just passable that thermoplastic resin is applied the shearing force that can separate the carbon nano-fiber that has condensed.
Disperse to be dispersed in the thermoplastic resin and to mix the carbon fibre composite of both mixed processes (mixing, dispersion step) acquisitions by above-mentioned making with particle and carbon nano-fiber, can be by implementing injection moulding, compression forming, extrusion modling etc., processing and forming is the shape of expectation.Compression forming for example comprises the steps:, will disperse the carbon fibre composite with particle and carbon nano-fiber to be placed in the mould that is set to uniform temperature with intended shape, process certain hour moulding under pressurized state.
In the mixing of thermoplastic resin and carbon nano-fiber, dispersion step, perhaps after, can be added in the known additive that is adopted in the processing of thermoplastic resin usually.For example can list as additive: antioxidant, releasing agent, pigment, plasticiser, anti-live agent, strengthening material, fire retardant etc.
In addition, in the above-described embodiments, adopt identical mixing method to implement operation (a) and operation (b), but, be not limited to this, for example also can be operation (a) with granular thermoplastic resin and disperse to do after the mixing, join in the multishaft extruder of operation (b) with particle.
(E) carbon fibre composite that obtains by said method
The carbon fibre composite of present embodiment is that carbon nano-fiber is evenly dispersed in the thermoplastic resin as base material.This state also can be described as the state that thermoplastic resin is being limited by carbon nano-fiber.In this state, not compared by the situation of carbon nano-fiber restriction, diminished by the motility of the thermoplastic resin molecule of carbon nano-fiber restriction with thermoplastic resin.Therefore, the spin-spin relaxation time (T2s) of first composition of the carbon fibre composite that present embodiment is related, the spin-spin relaxation time (T21) of second composition and spin-lattice relaxation time (T1), shorten than the situation of the thermoplastic resin alicyclic monomer that does not comprise carbon nano-fiber.When particularly mixing carbon nano-fiber in comprising the dispersion usefulness thermoplastic resin of particle, compare with the situation of the thermoplastic resin that only comprises carbon nano-fiber, the spin-spin relaxation time (T21) of second composition shortens.In addition, the spin-lattice relaxation time (T1) of carbon fibre composite changes pro rata with the combined amount of carbon nano-fiber.
In addition, under the state that the thermoplastic resin molecule is limited by carbon nano-fiber,, can think that second composition (the not composition that is limited by the molecule of the skeleton chain) reduces based on following reason.Promptly, if make the reducing of transport properties of molecules globality of thermoplastic resin owing to carbon nano-fiber, can think that based on underlying cause second composition reduces: the part that second composition can not easily move increases, and with first composition equal behavior takes place easily; In addition, because second composition moves easily, adsorbed by the activated centre of carbon nano-fiber easily so become.Therefore, compare with the situation of the thermoplastic resin alicyclic monomer that does not comprise carbon nano-fiber, the composition branch rate (f1, ratio) of composition with spin-spin relaxation time of second composition diminishes.Particularly compare with the situation of the thermoplastic resin that comprises carbon nano-fiber, disperse when mixing carbon nano-fiber in the thermoplastic resin of particle comprising, the composition branch rate (f1) of composition with spin-spin relaxation time of second composition further diminishes.
Based on the above, the measured value that the related carbon fibre composite of present embodiment obtains by the Hahn's echo method that adopts PULSED NMR is preferably in following scope.
Promptly, in carbon fibre composite, it was 100 to 1000 μ seconds preferably in the spin-spin relaxation time (T2s) of first composition of 250 ℃ of mensuration, spin-spin relaxation time (T21) of second composition or do not exist or less than 2000 μ seconds, and the composition branch rate (f1) of composition of spin-spin relaxation time with second composition is for less than 0.2.
The spin-lattice relaxation time (T1) that determines by the Hahn's echo method that adopts PULSED NMR be the same with the spin-spin relaxation time (T2) be the yardstick of the transport properties of molecules of expression material.The concrete spin-lattice relaxation time that we can say thermoplastic resin, the motility of short molecule was low more more, and thermoplastic resin is hard more, and the motility of long more molecule of spin-lattice relaxation time is high more, and thermoplastic resin is soft more.
The carbon fibre composite that present embodiment is related, the flowing temperature in the temperature dependency of dynamic viscoelastic is measured is preferably than the high temperature more than 20 ℃ of flowing temperature of raw material thermoplastic resin alicyclic monomer.The carbon fibre composite of present embodiment is to disperse very well to be dispersed in the thermoplastic resin with particle and carbon nano-fiber.This state can be described as the state that aforesaid thermoplastic resin is limited by carbon nano-fiber.Under this state, thermoplastic resin is compared with the situation that does not comprise carbon nano-fiber, and its molecular motion diminishes, and the result is mobile the reduction.Owing to have such flowing temperature characteristic, the temperature dependency of the dynamic viscoelastic of the carbon fibre composite of present embodiment diminishes, and the result can have good hear resistance.
As mentioned above, the carbon fibre composite of present embodiment not only can be used as thermoplastic resin material but also can be used as metal or the raw material of composite such as nonmetal uses.Usually, the mutual complexing of carbon nano-fiber and having is difficult to the character of disperseing in medium.But, if the carbon fibre composite of the present embodiment raw material as metallic composite is used, so, because carbon nano-fiber exists with dispersity in thermoplastic resin, so by with this raw material and metal or matrix material displacement such as nonmetal, carbon nano-fiber can easily disperse in medium.
(F) manufacture method of carbon fiber-metal composite material or carbon fiber composite non-metallic material
The manufacture method of the carbon fiber-metal composite material in the present embodiment also has the operation (c-1) that the matrix material of the described thermoplastic resin of the carbon fibre composite that will obtain by described operation (b) and metal is replaced.
In addition, the manufacture method of the carbon fiber composite non-metallic material in the present embodiment also has the described thermoplastic resin of the carbon fibre composite that will obtain by described operation (b) and the operation (c-2) that nonmetallic matrix material is replaced.
Described operation (c-1) and operation (c-2) for example can adopt following various forming methods.
(powder compacting method)
Can carry out the powder compacting operation to the carbon fibre composite that obtains by described operation (b).The carbon fibre composite that for example directly will obtain by the foregoing description or the particle of freezing chippy carbon fibre composite contract at mould inner pressure specifically, under the sintering temperature (when for example dispersion is aluminium with particle is 550 ℃) of disperseing, calcine, thereby can obtain carbon fiber-metal composite material and carbon fiber composite non-metallic material with particle.
Powder compacting in the present embodiment is identical with the moulding of metal forming processed powders, that is to say and comprise so-called metal dust, and be not limited only to use the situation of powder stock, also comprise the formed block raw material of carbon fibre composite precommpression moulding in advance.Except general sintering process, can also adopt the discharge plasma sintering method (SPS) of use plasma agglomeration device etc. as sintering process.
In addition, with carbon fibre composite with become the metal material of matrix of carbon fiber-metal composite material or carbon fiber composite non-metallic material or after the particle of nonmetallic materials carries out wet mixed, can obtain carbon fiber-metal composite material and carbon fiber composite non-metallic material thereby carry out sintering equally.In this case, preferred mixed carbon fibre composite (wet mixed) in the particle of the matrix material of other in solvent.
And; the particle of freezing chippy carbon fibre composite is mixed with the particle of metal material that becomes matrix or nonmetallic materials; for example after doing mixing; in mould, carry out compression forming, obtain carbon fiber-metal composite material or carbon fiber composite non-metallic material by sintering process then.
Carbon fiber-metal composite material or carbon fiber composite non-metallic material by such powder compacting produces can make carbon nano-fiber be dispersed in the middle of the glass.The employed metal material of matrix or the particle of nonmetallic materials of becoming in this operation (c), preferably be used to obtain the employed dispersion of carbon fibre composite with the identical material of particle, can suitably select the size of particle according to the composite material that obtains by powder compacting or the purposes of composite non-metallic material etc.
(casting)
The casting method of carbon fiber-metal composite material or carbon fiber composite non-metallic material, can implement by following operation: will be blended into by the carbon fibre composite that described operation (b) obtains as the motlten metal of matrix or fusion nonmetal in, in having the mould of desirable shape, cast.
Such casting process can adopt the die casting method, casting die, the low pressure casting method that for example inject motlten metal or the nonmetal enforcement of fusion in the mold of steel.Can adopt utilizing thixo casting method that high-pressure trend makes its high pressure casting that solidifies, fused solution is stirred, utilizing centrifugal force that fused solution is cast centre spinning in the mold into etc. of the special casting classification that belongs to other in addition.
In these castings, make carbon fibre composite be blended in motlten metal or fusion nonmetal in, it is directly solidified in mold with this state, thereby makes carbon fiber-metal composite material or the moulding of carbon fiber composite non-metallic material.In addition, in this casting process, the thermoplastic resin of carbon fibre composite is replaced into motlten metal or fusion is nonmetal when being decomposed, removing by motlten metal or the nonmetallic temperature of fusion.
The employed motlten metal of casting process, can for example process employed metal from common casting: aluminium and alloy thereof, magnesium and alloy thereof, titanium and alloy thereof etc., in just so-called light metal and the light-alloy, suitably select a kind of or its combination according to purposes.
The employed fusion of casting process is nonmetal, can process employed nonmetal for example pottery or the glass from common casting, suitably selects a kind of or its combination according to purposes.
In addition, the metal that fused solution adopted is to comprise and be pre-mixed at the dispersion of the carbon fibre composite alloy with identical metal of particle or identical metallic element, therefore, can improve and the wellability of disperseing, can also improve the intensity of product carbon fiber-metal composite material with particle.In addition, under the nonmetallic situation of fusion, by comprising and disperseing also can to obtain same effect with the identical nonmetal or identical nonmetalloid of particle.
(osmosis)
Be penetrated in the carbon fibre composite making fused solution in the present embodiment below with reference to Fig. 1 and Fig. 2, the operation that the non-pressurised osmosis of just so-called employing is cast describes.
Fig. 1 and Fig. 2 utilize non-pressurised osmosis to make the structural representation of the device of carbon fiber-metal composite material.The carbon fibre composite that obtains in the foregoing description can use carbon fibre composite 4, and this carbon fibre composite 4 is to have for example compression forming in the mould of final products shape of desirable shape.
Fig. 1 is illustrated in the carbon fibre composite 4 (for example sneak at thermoplastic resin 30 and disperse with particle 50 and carbon nano-fiber 40) of putting into moulding in the airtight container 1.Configuration metal derby or nonmetal 5 above this carbon fibre composite 4.
Then, by being built in heater not shown in the container 1, to being placed on carbon fibre composite 4 and metal derby or nonmetal 5 heating of implementing to be higher than this material fusing point in the container 1.Metal derby after the heating or nonmetal 5 fusion become motlten metal or fusion is nonmetal.In addition, be decomposed and generating gasification with thermoplastic resin 30 in motlten metal or the nonmetal carbon fibre composite that contacts 4 of fusion, motlten metal or fusion be nonmetal to be penetrated into thermoplastic resin 30 vacancy that the back forms that is decomposed, thereby replaces.
As the carbon fibre composite 4 of present embodiment, utilize capillarity to make motlten metal or the nonmetal whole space that is decomposed to form at thermoplastic resin 30 of permeating as soon as possible of fusion.Under the situation of disperseing with the surface oxidation of particle, utilize that capillarity motlten metal or fusion are nonmetal to be penetrated into wellability has taken place to improve by being reduced dispersion with between the particle 50, and the inside of soaking full carbon fibre composite fully.
Then, stop the heating of the heater of container 1, and make in the composite material 4 infiltration motlten metal or the nonmetal cooling of fusion, solidify, thereby can make carbon nano-fiber 40 even dispersed carbon fiber-metal composite material or carbon fiber composite non-metallic materials 6.Carbon fibre composite that casting process adopted 4 is preferred to adopt the dispersion identical with employed motlten metal or the nonmetallic material of fusion in the casting process in advance to carry out processing and forming with particle.By such operation, can obtain the nonmetal homogeneous composite material that is easy to mix with particle with dispersion of motlten metal or fusion.
In addition, before heating container 1, also can vacuumize by the decompressor 2 (for example vavuum pump) that is connected container 1.And, can also in container 1, import nitrogen from the inert gas injection device 3 (for example nitrogen cylinder) that is connected on the container 1.
As everyone knows, for example, when dispersion was all adopted aluminium with particle and motlten metal, because the surperficial oxide of alumina particles 42 and aluminium block 5 covers, the wellability of the two was bad.But in the present embodiment, the wellability of the two is fine.That is because make molten aluminum when infiltration, and the molecule front end of the thermoplastic resin that has been thermal decomposited becomes atomic group, and by this atomic group, the oxide (aluminium oxide) on aluminium block 5 and alumina particles 42 surfaces is reduced.
Therefore, in the present embodiment, owing to can make the inner reducing gas that generates by the decomposition that is included in the thermoplastic resin in the carbon fibre composite, so, need not can implement cast by non-pressurised osmosis as the process chamber that prior art is prepared reducing gas.Like this, the wellability of the surface of the alumina particles that has been reduced and the molten aluminum that permeated has improvement, can obtain the integration metal material or the nonmetallic materials of homogeneous more.
In addition, since the mobile carbon nano-fiber that makes that the infiltration of molten aluminum produces invade in the alumina particles.And by the atomic group of the thermoplastic resin molecule that has been decomposed, the surface of carbon nano-fiber is activated, improved the wellability with molten aluminum.The carbon fiber-metal composite material of Huo Deing has the carbon nano-fiber in the matrix that is dispersed in aluminium like this.In addition,, can prevent the oxidation of molten aluminum in inert gas, further improve the wellability of alumina particles because this casting process is implemented.
In addition, more than be that in the above-described embodiments non-pressurised osmosis is illustrated, still,, for example also can adopt the pressure of the atmosphere gas that utilizes inert gas etc. to implement the pressurization osmosis of pressurization so long as osmosis just is not limited to this.
(embodiment)
Below, embodiments of the invention are narrated, but the present invention is not limited to this.
(embodiment 1-3, comparative example 1)
(1) manufacturing of sample
(a) manufacturing of carbon fibre composite
Operation (a): in first loading hopper of twin (double) screw extruder (250 ℃ of cartridge heater temperature), add the thermoplastic resin particle (100 weight portion) of the scheduled volume shown in the table 1, thermoplastic resin generation fusion then.
To the thermoplastic resin that is in this molten condition, add the dispersion particle of the amount of Table 1 (weight portion) from second loading hopper of twin (double) screw extruder, and make the double-shaft spiral rotation.
Operation (b): then, add the carbon nano-fiber (table 1 be recited as " CNT ") of the amount of Table 1 (weight portion) with dispersion with the 3rd loading hopper of the twin (double) screw extruder of particle from having mixed this thermoplastic resin, and make the double-shaft spiral rotation.
The carbon fibre composite that will squeeze out from the front end conduit of twin (double) screw extruder imports in being cooled to the mould of room temperature, thus the sample of the carbon fibre composite of the embodiment 1～3 of acquisition formation definite shape.
In addition, omit the adding of the dispersion usefulness particle in the above-mentioned operation (a), obtain the thermoplastic resin sample of comparative example 1.
Operation (c): the manufacturing of carbon fiber-metal composite material
The carbon fibre composite sample that obtains among above-mentioned (a) embodiment 1～3 is configured in the container (stove), aluminium block (feed metal) is placed on it, in inert gas (nitrogen), be heated to the melting point of aluminium.Aluminium block generation fusion becomes the aluminium fused solution, and in order to replace with the thermoplastic resin of carbon fibre composite sample, motlten metal permeates.After making aluminium fused solution infiltration, it is cooled off naturally it is solidified, thereby acquisition aluminium is the carbon fiber-metal composite material of matrix.In addition, the carbon nano-fiber that the combined amount of carbon nano-fiber is set in carbon fiber-metal composite material is 1.6vol%.
In addition, as the dispersion particle of embodiment 1～3, adopted alumina particles (average grain diameter: 28 μ m).Carbon nano-fiber adopts is that average diameter (fiber footpath) is about the carbon nano-fiber that 13nm, average length are about 25 μ m.
(2) mensuration of employing PULSED NMR
For each carbon fibre composite sample, measure by the Hahn's echo method that adopts PULSED NMR.This mensuration is to adopt " JMN-MU25 " of NEC's (strain) system to carry out.Mensuration is to be at observing nuclear
1H, resonant frequency are 25MHz, carry out under the condition that 90 ° of pulse widths are 2 μ sec, the pulse train (90 ° of x-Pi-180 ° of x) by Hahn technique thus Pi is carried out various variations measures attenuation curves.In addition, sample is to insert coupon to measure to the proper range in magnetic field.Measure temperature and be the temperature (250 ℃) when mixing in the operation (b).Utilize this mensuration obtain raw material thermoplastic resin alicyclic monomer and composite the carbon fibre composite sample first composition spin-spin relaxation time (T2s), second composition the spin-spin relaxation time (T21), have the composition branch rate (f1) and the spin-lattice relaxation time (T1) of the spin-spin relaxation time composition of second composition.Obtain in addition under measuring the situation that temperature is the temperature (250 ℃) when mixing in the operation (B), the spin-spin relaxation time (T2s) of first composition of raw material thermoplastic resin alicyclic monomer, the spin-spin relaxation time (T21) of second composition, have the composition branch rate (f1) and the spin-lattice relaxation time (T1) of the spin-spin relaxation time composition of second composition.Measurement result is as shown in table 1.The spin-spin relaxation time (T2s) of first composition of the carbon fibre composite sample of embodiment 1 be the spin-spin relaxation time (T21) of 680 (μ sec), second composition be 12000 (μ sec), to have the composition branch rate (f1) of composition of the spin-spin relaxation time of second composition be 0.12.The spin-spin relaxation time (T2s) of first composition of the carbon fibre composite sample of embodiment 2 is that spin-spin relaxation time (T2s) of first composition of the carbon fibre composite sample of 430 (μ sec), embodiment 3 is 350 (μ sec).Do not detect the spin-spin relaxation time (T21) of second composition among the embodiment 2,3.Therefore, having the composition branch rate (f1) of composition of the spin-spin relaxation time of second composition is 0 (zero).
(3) mensuration of E ' (dynamic viscoelastic rate)
Utilize JIS K 6521-1993 the carbon fibre composite sample of composite to be carried out the mensuration of E '.Its result represents in table 1.(4) utilize electron microscope (SEM) to observe
Utilize electron microscope that the carbon fibre composite sample and the carbon fiber-metal composite material sample of embodiment 1～3 and comparative example 1 are observed, observed result is represented in table 1.
(5) mensuration of compression endurance
The carbon fiber-metal composite material sample has been carried out the mensuration of compression endurance (Mpa).The mensuration of compression endurance is 0.2% (σ 0.2) endurance when compressing with 0.01mm/min of the test raw material with 10 * 10 * 5mm.
Table 1
| Embodiment 1 | | | Comparative example 1 | |||
| The raw material thermoplastic resin | Thermoplastic resin | | ABS | Polyamide | 6 | ABS |
| Mean molecule quantity | 150,000 | 150,000 | 120,000 | 150,000 | ||
| T2s(μsec)/250℃ | 1000 | 1000 | 800 | 1000 | ||
| T21(μsec)/250℃ | 25000 | 25000 | 12000 | 25000 | ||
| f1(μsec)/250℃ | 0.55 | 0.55 | 0.37 | 0.55 | ||
| T1(msec)/250℃ | 880 | 880 | 250 | 880 | ||
| Cooperate | Thermoplastic resin (weight portion) | 100 | 100 | 100 | 100 | |
| Disperse with particle (weight portion) | 20 (aluminium oxide) | 500 (aluminium oxide) | 500 (aluminium oxide) | 0 | ||
| CNT (weight portion) | 4 | 10 | 10 | 1.8 | ||
| Carbon fibre composite (thermoplastic resin is a matrix) | T2s(μsec)/250℃ | 680 | 430 | 350 | 1100 | |
| T21(μsec)/250℃ | 12000 | - | 0 | 28000 | ||
| fl(μsec)/250℃ | 0.12 | 0 | 0 | 0.58 | ||
| T1(msec)/250℃ | 410 | 330 | 100 | 900 | ||
| E’(30℃)(Mpa) | 10 | 28 | 67 | 3.2 | ||
| The dispersity of CNT (SEM observation) | Well | Well | Well | Bad | ||
| Carbon fiber-metal composite material (aluminium is matrix) | The dispersity of CNT (SEM observation) | Well | Well | Well | Bad | |
| Compression endurance (Mpa) | 350 | 420 | 450 | 65 | ||
| (vol% of CNT) | 1.6 | 1.6 | 1.6 | 1.6 |
According to embodiments of the invention 1～3, from table 1, can confirm the following fact.Promptly comprise the spin-spin relaxation time (T2s and T21/250 ℃) of carbon fibre composite sample 250 ℃ under of disperseing, and do not comprise dispersion and compare and to lack with the raw material thermoplastic resin of particle with particle and carbon nano-fiber.In addition, the composition branch rate (f1/250 ℃) that comprises the carbon fibre composite sample of metallic particles and carbon nano-fiber disperses to compare little with the raw material thermoplastic resin of particle and carbon nano-fiber with not comprising.From these data as can be seen carbon nano-fiber be dispersed in well the related carbon fibre composite of embodiment.
Just can most clearly know this fact by comparing embodiment 1 and comparative example 1: promptly do not comprising dispersion with in the comparative example 1 of particle, the spin-spin relaxation time of carbon fibre composite sample (T2s and T21/250 ℃) is compared with the situation of raw material thermoplastic resin alicyclic monomer and is not had what difference basically.And in embodiments of the invention 1, the spin-spin relaxation time of carbon fibre composite sample (T2s and T21/250 ℃) is compared with the situation of raw material thermoplastic resin alicyclic monomer and has lacked a lot.In addition, composition branch rate (f1/250 ℃) is also drawn same result.
In addition, from the result of the E ' that used the carbon fibre composite sample, can confirm in embodiments of the invention 1～3, to have improved dynamic viscoelastic, and because the dispersion of carbon nano-fiber has obtained the enhancing effect owing to comprise carbon nano-fiber.Just can most clearly know this fact by comparing embodiment 1～3 and comparative example 1.
In addition, observed result according to the electron microscope (SEM) of the carbon fibre composite sample of embodiment 1～3 and comparative example 1 and carbon fiber-metal composite material sample, in the sample of embodiment 1～3, the dispersion of carbon nano-fiber in order, in the sample of comparative example 1, the cohesion of observing carbon nano-fiber is a lot, and the dispersion situation is bad.
And the compression endurance of the carbon fiber-metal composite material sample of embodiment 1～3 and comparative example 1 improves, and can know that thus carbon nano-fiber is dispersed in the matrix well.
Can know that from above situation by the present invention, the carbon nano-fiber that generally is difficult to be scattered in the base material is evenly dispersed in the thermoplastic resin, thereby obtain the carbon fiber-metal composite material of even dispersed carbon nanofiber.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
The symbol explanation
1 container, 2 decompression devices
3 inject device 4 carbon fiber composite material
5 metal derbies or nonmetal
6 carbon fiber-metal composite materials or carbon fiber composite non-metallic material
30 thermoplastic resins, 40 carbon nano-fibers
50 disperse to use particle
Claims (38)
1. carbon fibre composite comprises:
Thermoplastic resin;
Carbon nano-fiber is dispersed in the described thermoplastic resin; And
Disperse to use particle, be used for promoting dispersion at described thermoplastic resin carbon nano-fiber.
2. carbon fibre composite according to claim 1, wherein, with respect to described thermoplastic resin 100 weight portions, described dispersion particle is 1～2000 weight portion.
3. carbon fibre composite according to claim 1, wherein, described dispersion has the average grain diameter bigger than the average diameter of described carbon nano-fiber with particle.
4. carbon fibre composite according to claim 1, wherein, described dispersion is smaller or equal to 500 μ m with the average grain diameter of particle.
5. carbon fibre composite according to claim 1, wherein, described dispersion particle is a metallic particles.
6. carbon fibre composite according to claim 1, wherein, described dispersion particle is a non-metallic particle.
7. carbon fibre composite according to claim 5, wherein, described metallic particles is light metal particle or this light metal alloy particle of selecting from aluminium, magnesium, titanium.
8. carbon fibre composite according to claim 1, wherein, the molecular weight of described thermoplastic resin is 10,000 to 1,000,000.
9. carbon fibre composite according to claim 1, wherein, the average diameter of described carbon nano-fiber is 0.5 to 500nm.
10. a carbon fiber-metal composite material is used the described thermoplastic resin of the matrix material displacement of metal according to each the described carbon fibre composite in the claim 1 to 9.
11. a carbon fiber composite non-metallic material is with the described thermoplastic resin of nonmetallic matrix material displacement according to each the described carbon fibre composite in the claim 1 to 9.
12. the manufacture method of a carbon fibre composite comprises:
Operation (a) is with thermoplastic resin and be used for promoting that carbon nano-fiber mixes with particle in the dispersion of the dispersiveness of this thermoplastic resin; And
Operation (b) is blended in described carbon nano-fiber and comprises described dispersion with in the described thermoplastic resin of particle, and utilizes shearing force that described carbon nano-fiber is disperseed.
13. the manufacture method of carbon fibre composite according to claim 12, wherein, with respect to thermoplastic resin 100 weight portions, described dispersion particle is 1～2000 weight portion.
14. the manufacture method of carbon fibre composite according to claim 12, wherein, described dispersion has the average grain diameter bigger than the average diameter of described carbon nano-fiber with particle.
15. the manufacture method of carbon fibre composite according to claim 12, wherein, described dispersion is smaller or equal to 500 μ m with the average diameter of particle.
16. the manufacture method of carbon fibre composite according to claim 12, wherein, described dispersion particle is a metallic particles.
17. the manufacture method of carbon fibre composite according to claim 12, wherein, described dispersion particle is a non-metallic particle.
18. the manufacture method of carbon fibre composite according to claim 16, wherein, described metallic particles is light metal particle or this light metal alloy particle of selecting from aluminium, magnesium, titanium.
19. the manufacture method of carbon fibre composite according to claim 12, wherein, the molecular weight of described thermoplastic resin is 10,000 to 1,000,000.
20. the manufacture method of carbon fibre composite according to claim 12, wherein, the spin-spin relaxation time (T2s) of first composition under the temperature of the described operation (b) measured by the Hahn's echo method that adopts PULSED NMR of described thermoplastic resin was 100 to 50000 μ seconds.
21. the manufacture method of carbon fibre composite according to claim 12, wherein, the spin-lattice relaxation time (T1) of first composition under the temperature of the described operation (b) measured by the Hahn's echo method that adopts PULSED NMR of described thermoplastic resin was 10 to 5000m seconds.
22. the manufacture method of carbon fibre composite according to claim 12, wherein, the average diameter of described carbon nano-fiber is 0.5 to 500nm.
23. the manufacture method of carbon fibre composite according to claim 12, wherein, described operation (b) adopts open type roller method to carry out.
24. the manufacture method of carbon fibre composite according to claim 12, wherein, described operation (b) adopts the mixing method of closed to carry out.
25. the manufacture method of carbon fibre composite according to claim 12, wherein, described operation (b) employing multiaxis pushes mixing method to carry out.
26. the manufacture method of a carbon fiber-metal composite material also comprises the operation (c-1) that the matrix material of the described thermoplastic resin of the carbon fibre composite that will obtain by the described manufacture method of claim 12 and metal is replaced.
27. the manufacture method of a carbon fiber composite non-metallic material also comprises the described thermoplastic resin of the carbon fibre composite that will obtain by the described manufacture method of claim 12 and the operation (c-2) that nonmetallic matrix material is replaced.
28. the manufacture method of carbon fiber-metal composite material according to claim 26, wherein, described operation (c-1) is a powder compacting.
29. the manufacture method of carbon fiber composite non-metallic material according to claim 27, wherein, described operation (c-2) is a powder compacting.
30. the manufacture method of carbon fiber-metal composite material according to claim 26, wherein, described operation (c-1) is that described carbon fibre composite is blended in the motlten metal, the operation of casting in having the mold of intended shape.
31. the manufacture method of carbon fiber composite non-metallic material according to claim 27, wherein, described operation (c-2) be with described carbon fibre composite be blended into fusion nonmetal in, the operation of in having the mold of intended shape, casting.
32. the manufacture method of carbon fiber-metal composite material according to claim 26, wherein, described operation (c-1) is included in the operation of the top placement metal derby of described carbon fibre composite; And make its fusion become motlten metal by heating described metal derby, make the described thermoplastic resin gasification in the described carbon fibre composite simultaneously, motlten metal is permeated, thus the operation that described thermoplastic resin and described motlten metal are replaced.
33. the manufacture method of carbon fiber composite non-metallic material according to claim 27, wherein, nonmetal operation is placed in the top that described operation (c-2) is included in described carbon fibre composite; And by heating described nonmetal to make its fusion become fusion nonmetal, make the described thermoplastic resin volatilization in the described carbon fibre composite simultaneously, make that fusion is nonmetal permeates, thereby with described thermoplastic resin and the nonmetal operation of replacing of described fusion.
34. the manufacture method of carbon fiber-metal composite material according to claim 26, wherein, described matrix material is and the described dispersion identical material of particle.
35. the manufacture method of carbon fiber composite non-metallic material according to claim 27, wherein, described matrix material is and the described dispersion identical material of particle.
36. carbon fibre composite by each the described manufacture method machine-shaping in the claim 12 to 25.
37. carbon fiber-metal composite material by the described manufacture method machine-shaping of claim 26.
38. carbon fiber composite non-metallic material by the described manufacture method machine-shaping of claim 27.
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| JP2004153428A JP4245514B2 (en) | 2004-05-24 | 2004-05-24 | Carbon fiber composite material and method for producing the same, method for producing carbon fiber composite metal material, method for producing carbon fiber composite non-metal material |
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| US (1) | US7438970B2 (en) |
| EP (3) | EP1600469B1 (en) |
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-
2004
- 2004-05-24 JP JP2004153428A patent/JP4245514B2/en not_active Expired - Fee Related
-
2005
- 2005-05-23 EP EP20050253157 patent/EP1600469B1/en not_active Ceased
- 2005-05-23 US US11/134,292 patent/US7438970B2/en active Active
- 2005-05-23 EP EP10184625.1A patent/EP2287237B1/en not_active Ceased
- 2005-05-23 EP EP10184607.9A patent/EP2314641B1/en not_active Ceased
- 2005-05-24 CN CNB2005100720554A patent/CN100544946C/en not_active Expired - Fee Related
- 2005-05-24 KR KR1020050043685A patent/KR100695737B1/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101778713B (en) * | 2007-08-16 | 2013-08-14 | 空中客车英国运营有限责任公司 | Method and apparatus for manufacturing a component from a composite material |
| CN101960061B (en) * | 2008-03-07 | 2013-03-06 | 西门子公司 | Strand-like material composite with cnt yarns and method for the manufacture thereof |
| CN101781471B (en) * | 2009-01-16 | 2013-04-24 | 鸿富锦精密工业（深圳）有限公司 | Composite material, electronic product outer casing adopting same and manufacturing method thereof |
| CN106182798A (en) * | 2009-11-06 | 2016-12-07 | 波音公司 | Compression mod preparation method and the thermoplastic component of enhancing thus moulded |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2314641B1 (en) | 2017-03-29 |
| EP1600469B1 (en) | 2012-04-18 |
| EP2287237A1 (en) | 2011-02-23 |
| EP2314641A1 (en) | 2011-04-27 |
| JP4245514B2 (en) | 2009-03-25 |
| KR100695737B1 (en) | 2007-03-15 |
| JP2005336235A (en) | 2005-12-08 |
| EP2287237B1 (en) | 2017-03-29 |
| EP1600469A1 (en) | 2005-11-30 |
| CN100544946C (en) | 2009-09-30 |
| KR20060048080A (en) | 2006-05-18 |
| US7438970B2 (en) | 2008-10-21 |
| US20060062986A1 (en) | 2006-03-23 |
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